Flexible alumina (Al2O3)/carbon (C) composite nanofibers film has been fabricated via electrospinning, followed by pre-oxidation and carbonization. Polyacrylonitrile (PAN)/Polyvinylpyrrolidone (PVP) and aluminum hydroxyacetate (Al(OH)C4H6O4) acted as carbon precursor and Al2O3 precursor, respectively. The obtained Al2O3/C nanofibers films were systematically characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FTIR), energy dispersive spectrometer (EDS), X-ray diffractometer (XRD) and flexural tests. The results indicated that Al2O3/C composite nanofibers with rough surface consisted of graphitic phase and gamma-Al2O3 phase. The Al2O3 covering on the surface of nanofibers improved the flexibility of carbon nanofibers (CNFs) film. Moreover, with the amount of Al2O3 increasing, both flexural rigidity and flexural modulus of Al2O3/C nanofibers film decreased drastically. In the other words, the flexibility of CNFs film improved greatly. The Al2O3/C nanofibers film with the mass ratio of Al(OH) C4H6O4: PAN being 4: 1 exhibited flexural modulus that was about 11 times lower than that of CNFs film without Al2O3, suggesting that the highly flexible Al2O3/C nanofibers film was obtained.